CA2163402A1 - Thixotropic polyurea compositions - Google Patents
Thixotropic polyurea compositionsInfo
- Publication number
- CA2163402A1 CA2163402A1 CA002163402A CA2163402A CA2163402A1 CA 2163402 A1 CA2163402 A1 CA 2163402A1 CA 002163402 A CA002163402 A CA 002163402A CA 2163402 A CA2163402 A CA 2163402A CA 2163402 A1 CA2163402 A1 CA 2163402A1
- Authority
- CA
- Canada
- Prior art keywords
- polyurea composition
- molecular weight
- polyether
- polyurea
- diamine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/02—Polyureas
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2190/00—Compositions for sealing or packing joints
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Disclosed herein are polyurea compositions comprising the reaction product of: (a) a polyphenyl polymethylene polyiso-cyanate or a urea-modified prepolymer thereof and (b) a mixture of amines comprising (i) aminocrotonate polyether, and (ii) a low molecular weight aromatic or cycloaliphatic diamine or mixture thereof.
By selecting appropriate blends of aminocrotonate polyethers and low molecular weight polyamines, it is now possible to design all-urea formulations with non-sagging performance.
By selecting appropriate blends of aminocrotonate polyethers and low molecular weight polyamines, it is now possible to design all-urea formulations with non-sagging performance.
Description
Mo41 72 THIXOTROPIC pOl YUPF~ COMPOSITIONS
BACKGROUNC~ OF THE INVENTION
Field of the Invention:
The present invention relates to polyurea cor"positiGns derived from polyphenyl polymethylene polyisocyanate and a select group of ar":. ,es.
5 Brief Desc,~iol1 of the Prior Art:
Non-sagyins~ (or thixotropic) cGmpositions are widely known and used col"n~ercially. Such ",ater;als are important bec~use they are very convenient to use in many applications. An example would be adhesives and sealanl~ used in autom~ti~/e manufacturing where 10 such formuhliol,s can be supplied and conveniel,lly manipulated in a low-viscosity liquid form but then applied to even vertical surfaces as a thick non-running ",aterial.
Polyureas are also generally known in the art. CG"")ar~d to polyu,~tl,al-e analogs polyureas can have superior physical 15 prope,lies such as high te",per~lure pe,rul",al,ce~ adl,esion oil and solvent ,t:sista"ce and tear sllellylll. Due to the very high reactivity of most amine cGr"pounds toward isocyandles polyurea formulaliol)s often have short gel-times resulting in short "pot-life" (or working time). Therefore polyurea co",posilions have been limited to 20 applications where very short gel-times are desi,able such as in reaction injection molding. In additiol~ be~llse of the linli~lion to a fewfast-r~acti"ghigh-mo'ecul~rweightpolyar":.,es thereactivityand viscosity profiles of polyurea formulations could not be manipulated surr,cie.,lly to provide non-sagging systems.
ksl/11 2994 U.S. 5,128,433 ~JisclQses thixutlupic polymer compositiGn - comprising the reaction product of aromdtic polyisocyandles such a low rnclecu'A~ weight polyisocyanales based on 4,4'-diisocyanato-di~he"yl~"eti,al,e, toluene diisocyanate or the like or their prepolymers, and one or more ar~l"dtic diar"i.,es. The con,positio"s are said to be useful in ",al~i"g cGdlings, sealanls, adhesive bonds and molds.
U.S. Patent 4,954,199 disclQses a structural n,el"ber comprising a laminate and an adhesive where said adhesive is the reaction product of a speciried proportion of polyur~ll,alle-urea forming components: (a) 100 parts by weight of at least one hydroxyl functional ",alerial having a molecular weight of at least 300 and a hydroxyl f~n~;tio"ality of at least 2 and which ",al~rial is pre~r~bly selected from the group consisli"g of polyether polyols, polyester polyols, polyester amide polyols, and polycalLGI,ate polyols; (b) 0.2 to 20 parts by weight of an aliphatic, ar~mdlic, and/or a cycloaliphatic diamine or triamine; and (c) an organic isocyanate in an amount sufficient to render the isocyanate index between about 70 and about 150, wherein said cGmponent (c) is not pr~r~a-,ted with any of the components (a) and (b).
U.S. ratent~ 5,164,473 and 5,204,439 disclQse low viscosily two-cGIllpGllellt filled poly~ ll,ane adl,esives which are useful as structural adhesives cGnl~ lg a low viscosity isocyanate con"~onenl in a quantity sufficient to provide an isocyanate index of about 100 to 150 comprising an organic polyisocyanate wherein up to 10 equivalent percent of the isocyanate groups of said polyisocyanate have been ",odified by r~actiGn with one or more isocyanate-reactive compounds; a low viscosity curative component cGmprisi"g 5 to 50 equivalent per~enl of a polyether polyol and/or a polyether terminated Mo4172 by aro",dlic amino groups having an equivalent weight gr~aler than 500 based on the total equivalents of amino and hydroxyl groups of the curative co",po,)ent; 50 to 95 equivalent perce,lt of one or more chain e,~lel)del~ col"~.risi"g from 50 to 100 per~;enl of the isocyanate-reactive equivalents based on the total equivalents of amino and hydroxyl groups of the equivalent component; and one or more isocyanate-reactive diamines or triamines in a quantity surricie. ,t to produce adequate r~sistance to flow when the isocyanate and curative components are mixed and wherein at least one of these components contains at least one filler in a total quantity of from about 10 to about 40 percent by weight of the filled polyurethane adhesive.
During automobile manufacturing structural adhesives that are used to bond polymeric autol"ob.'e panels such as fascia can be subjected to te",per~ res of about 200 deylees Cenligrade or higher.
At these high ter"perdtures many of the art-related adhesives such as polyur~ll,ane adhesives loose their i"ley,ity by foaming cracl~i"y and/or softening with a conse4uential loss in physical and other adl ,esive prupel lies.
As would be realized there is a need for structural adhesives that can w;tl,stand high temper~lures.
SUMMARY OF THF INVFI~TION
Su,~l.risingly it was found that by using amir,ocr~tonated polyethers it is now possiLI~ to prepare blends containing only polyamine chain extenders and amine-terminated soft-sey",enl compounds with a balanced reactivity of the amines toward isocyalldles. It is ll,erefore possible in ,urd~;tice to prepare non-sagging all-urea cor"positions. Thus the desirable physical properties of polyureas can now be combined with non-sagg;"g chara~terislics.
Mo41 72 As would be re~ ed pr~pa(atiG,) of such cG"")ositi~ns demand highly controllable reactivity in order to opli",i,e viscosity profile hGI~ogeneily gel-time working life and green sl,e"~tl,. An u,lbalanced reactivity of the amines can also result in agglo~erdliGn 5 of urea upon mixing with the isocyanate. This leads to inhomogeneous n,dler;als and unacceplable physical properties. By the presenl invention one avoids the above problems bec~llse it is now possi~lc to prepare all-amine blends of chain extenders and soft seg",enls which provide improved reactivities and physical properties.
In accorlJance with the forego:.,g the present invention encompasses a polyurea composition comprising the reaction product of: (a) a polyphenyl polymethylene polyisocyanate or a urea-",GJiried prepolymer ll,ert:of and (b) an isocyanate reactive component comprising amines consislil,g essentially of (i) ar"inocr~tondte 15 polyether and(ii)alow",ole~ weightarol"~licoraliphatic diamine. The polyurea cGmpositiol, of the invention exhibits improved sag resislance at room ten,per~t.lre. This is manifested as a small bead of the rea.;ti"g ",aterial placed on a vertical surface not flowing sagging or dri~ping to make the ",dterial convenient to use in the 20 field. The polyurea composition are char~cteri,ed by markedly improved ll,e""al pelr~""ance properties.
DETAII Fn DFSCRIPTION OF THE INVFI~ITION
The polyurea cGI"positi~n of the invention can be pr~par~d by ,eacti"g the polyphenyl polymethylene polyi-~Gcyanate or a modified-25 urea prepolymer thereof with the mixture of amines of the invention inan equivalent ratio of the isocyanate to the amine in the range of about 0.9 to 1.4:1 and pr~:fer~bly 1.1:1 to 1.3:1.
The polyphenyl polymethylene polyisocyanate or the urea ",od~ried prepolymer thereof usually has an isocyanate contenl of Mo-41 72 about 20 to 40 pr~ferably 28 to 33. It can be obtained by pl,osgenating aniline/formaldehyde condensaliGn products. Examples Ll~er~or and their Illelhod of plt:pardliGn can be found in literature references such as Polyu,etl,ane I landbool; 2nd Edition G. Oertel 5 Hanser Publishers Munich Vienna NewYork pp: 73-83 and U.S.
Patents 3 471 543 which are i"co,~or~ted herein by ,~f~r~nce.
The urea-",o-l riecl prepolymer can be prtpar~d by r~a~ ti"g the polymeric polyphenyl polymethylene polyisocyanate with an amine.
Examples thereof and their ",ell,od of preparation are disclosed in 10 U.S. Patent 5 164 473 which is incorporated herein by ,ererence. The isocyanate reactive co"~pG"enl is a mixture of amines useful herein collsislil,g essentially of an aminocrutonate polyether and a low molecular weight arc""atic or aliphatic diamine. The aminocr~lonale polyether has a molecular weight of 500 to 5000 and pr~fer~bly 1000 15 to 3000 and a functionality of 2 to 6 and pr~ferably 2 to 3. The aminocr~tolldle polyether can be pr~par~d by aminolysis of ~cetoacelylated polyols. Ekdlllples thereof and their method of pr~:par~lion can be found in literature le~r~"ces such as U.S. Patents 3 691 112 3 666 726 5 066 824 and 5 151 470 which are 20 incorporated herein by refel~l)ce.
The low mc'ecul-~ weight dian,i"e has a ",olec~'-r weight of about 60 to 400 and pr~rably 60 to 300. Exar"ple. of the low Illo'e~ r weight ar~n,dlic diamine is s~lected from the group c~nsisli"g of toluene diamine diethyltoluene diamine 4 4'-diphenyl-25 methane diamine l,i",ell,ylene glycol di-p-ar":.,ol,el,~oale and bis(4-n-butylaminophenyl) ",ell,ane. Examples of the low r",olec~ weight aliphatic diamine is selectecl from the group cGnsi ti"g of isophorone diamine 4 4'-diamino-3 3'-dimethyldicyclohexyl~"ethane piperd~i"e bis-(4-aminocyclohexyl) ",~tl,ane and ethylenediamine.
Mo4172 In the pr)cess for pr~pa,i"g the polyurea composiliGn, the polyphenyl polymethylene polyisocyanate or the urea "odiried prepolymer lher~of and the mixture of amine can be combined in any order. Typically, the resulting combination (blend) is subjected to 5 isocyanate ~ddition r~actiG" at a"lbi~nl or elevated temperatures of up to 150C and p,efe,~bly 110 to 135C. Solvents which are typically inert solvents can be used for ease of rea~;tiGn. Although catalysts are not ordinarily required, they can be used, if desired. The ~aotio" product comprises the polyurea colllposiliGn of the invention.
In the practice of the invention, the polyurea col"position can be fommulated with additives such as fillers, Pis ",euts, molecular sieves, catalysts, and auxilialies such as flow agents, surface-active additives, anti-foaming agents, dyes, UV-stabilizers, fungi~l~lic and ba.,~rio~l~lic s~ sl~nces, such as those described in European 15 Patent Application 81,701 at column 6, line 40 to column 9, line 31.
Suitable fillers, particularly for the high temperature application (ll,e""al properties), include minerals, e.g. silicate-containing minerals, such as alltiy~lite~ sel~el,ti"e, homblends, amphiboles, chrysotile, talc, mica and kieselguhr; metal oxides such as kaolin, aluminum 20 oxides, titanium oxides, and iron oxides; metal salts such as chalk and heavy spar (barium sulfate); inGlyan.c ~iy"~ents such as cadmium sulfide and zinc sulfide; and glass, asbeslos powder, carbon fibers, and the like. Pl~rer,~d fillers are s~ sl~nlially inert under the col,ditions encountered when the components of the invention are 25 mixed. The pr~fel,ed fillers are talc, wollastonite or clay. A
particularly pr~rer,ed filler is talc. Fillers may be used either individual or in ad",i~ re. The fillers are added to either or both of compGnent~
(a) and (b) in quantities totaling about 10 to about 40% by weight based on the total quantity of the filled adhesive.
Mo-41 72 _ S~ le auxiliary agents and additives may include, for example, catalysts for the polyisocyanate-polyaddilio" ,~a~;tiG", drying agents, surface-active additives, anti-foaming agents, pigments, dyes, UV stabilizers, and pl~-~lic;~er~i. Typically, drying agents that avoid 5 rollndliol1 of bubbles that adversely affect high ter"perdl-lre pelroll''ance. Plefer~bly the drying agents are molecular sieve zeolites that can be employed in an amount of 1 to 15 parts by weight per 100 parts of the polyether polyol. Specific but nonlimiting examples of the m~'ecll~^r sieves can be sodium aluminosilicate in 10 amir,ocr~tondled polyether or polyether polyol (1:1) or sodium aluminosilicate powder.
In the practice of the invention, the isocyanate component is mixed with the isocyanate-reactive cGr"pol)enl in a predetermined ratio designed to provide an isocyanate index of from 100 to 150.
15 The term "isocyanate index" is defi"ed as the quotient, multipliei by 100, of the number of isocyanate groups divided by the number of isocyanate-reactive groups.
The polyisocyanate and the mixture of ar"i"es of the present invention are char~ctt:ri~ed by low viscosities As used herein, the 20 term "low viscosity" refers to a BroekfiEld viscosity at 25C of less than about 20,000 mPa-s. Despite the low vi3cosity, the reactive components exhibit excell~"l sag rt:sislance when the isocyanate and polyol blend are mixed.
The filler, as well as the G~ nal additives and auxiliaries, can 25 be mixed with either or both of the isocyanate component and the isocyanate-reactive component but is pre~er~bly mixed with the isocyanate-reactive component. The compol)ents may be mixed by any of various known ~ lhods, including impi"gel"enl mixing and Mo41 72 -static mixing and they may be arp'.ei to the sub~l,dle to be bonded as thin films or in the form of beads.
The polyurea compositiGns can be used in adhesive caulking and sealanl apr'.c^tions. It is pr~selltly preferred to employ the 5 polyurea ColllpoSitiGn in adhesive applic~lions for bonding .lirrarel)l or similar sul,sl,alas. The adhesivc can be used to bond sub~l,dles suchassteel aluminum polyl"~ll,ane epoxyorfiber-r~ rorl;ed polyester. The process for bonding the sulJ~lldtas cor"prises applying the adhesive to a subject sul)~tldla and conlacti"~ the surface with a 10 surface of another substrate to which is optionally applied the adhesive. The adl,esive can be ar plied by any convenient means such as in,pi.,gel"ent mixing or static mixing.
This and other ~-speGts of the invention are further illuslldted but are not i"tended to be limited by the following examples in which 15 all parts and per~nlages are by weight unless ull,elwi3e specifiad.
FxAMpl FS
AMINOCROTONATF POI YFTHFR SYNTHFSIS:
An amir,ocr~tondla polyether was p,t:pared using the following pr~ced.lre. Poly(l~l,ametl,yl~neoxide) diol (75.96 parts equivalent 20 weight 500) was r~actad with tert-butyl~ceto~cet~le (24.04 parts) at 175C under vacuum. After four hours FTIR analysis illdi~ted conlplete loss of the OH absGr~lion at 3300 cm~~. The room te,nper~ture viscosity was 520 mPa-s. This ~ceto~cetylated product (85.5 parts) was r~actad with cyclohexylamine (14.5 parts) at 110C
25 under vacuum. After several hours the product was cooled to room te",p~rdture (1790 mPa-s at 25C).
Exar,l~ le 1:
An amine blend according to the invention was prapal-ad using 63.5 parts cyclohexylamir,ocrotol,dle polyether (described above); 4.6 Mo~172 -g parts Ethacure 300 (Ethyl Corp.); 1.5 parts bis-(4-aminocyclohexyl)-",~tl,ane; 7.0 parts sodium aluminosilicate powder; 23.4 parts talc powder. This blend was ble.,Jed de~ssed and ,~acted at a 128 index with a polymeric di~Jl,enylm~ll,d"e diisocyanate (2 4'-isomer 5 conlenl about 1.6% and NCO functionality about 2.8). The ,t:actio"
mixture was bag mixed to avoid incorpordtion of air bubbles and a 6 x 6" x 1/8" plaque was cast. After curing the ",atelial at 100C for one day the Shore D I lar~ll,ess was 55. The sofleni"g point as determined using ll,el"~G",echanical analysis (TMA) was 168C.
10 Example ~:
An amine blend according to the invention was p,t:pared using 85.9 parts cyclohexylamir,ocrutonale polyether (desc,iued above); 2.2 parts piper~i"e; 1.7 parts diethyltoluene diamine; 10.0 parts sodium aluminosilicate powder. This mixture was blended degAssed and 15 reacted with the polyphenyl polymethylene polyisocyanate descl iL,ed in Ex~l~lplo 1. The rea~;tiol) was carried out at an NCO/OH ratio of 130. The rea~liol) blend was mixed cast and cured as described above for Exar"pl~ 1. The Shore A l lardl,ess of the resultant plaque was 35.
20 Example 3:
An amine blend accor~ling to the invention was prepaled using 63.3 parts cyclohexylamir,oc,ùtonale polyether (descliL,ed above); 7.5 parts llilll~:lhyle.,eylycol di-p-aminobel,~oate (Polacure 740M Air Products); 1.5 parts bis-(4-aminocyclol,exyl) metl,ane; 4.0 parts 25 sodium aluminosilicate powder; 23.7 parts talc. The mixture was ble.l-Jed de~ssed and reacted at an index of 130 with the polymeric polyisocyanate descriued in Example 1. After blendi"~ ca:,ling and curing as descriL,ed above the ",alerial hardness was 56 Shore D.
Mo-4172 -l ~ Shear Testing:
Adhesion pe,rullllance of Examples 1 2 and 3 was screened by using the lap shear test metl,ûd (SAE J1525). Saln~ les were prepared using sheet molding compound plaques (4" x 6" x 0.125") 5 and were bol)ded togetl,er using metal spacer:~ to insure a bond thickness of 0.030 inches. The bond overlap was 1 inch. The bond surface of the sheet molding compound was buffed with a clean d~
cloth prior to bonding to remove suRace conta,ninants. The sar"pl-s were cured in an oven at 135C for one hour and then conditioned at 10 room temperature for one day. Test coupons (4 x 1 in.) were cut from the cured plaques using a diamond-tipped saw. Samples were tested at room l~n,peldlure (ca. 23C). The maxi",um load values and %
sub~tldte failure meas~"e",enl:j are all averaS~es of five samples.
Test results are shown in the table below.
ADHESION TESTING RESULTS
ROOM TEMPERATURE LAP SHEAR TESTS
AdhesiveMaxi",um Load (PSI) % Subslr~ate Failure Example 1 686 100 Exall,pl~ 2622 100 Example 3 606 100 The results above clearly i".Jicale that these all-urea adhesive of this invention provide ex~e"ont bond strength to sheet molding cGl"pound. The maximum load values of 606 to 686 PSI show that these materials give sufficient adhesion to be classi~ied as high-25 peRormance (or"structural") adhesives. In addition the percentsuLst,ale failure measu,~l"ent~ prove that the adhesive and adhesive bond are stronger than the sul,:,l,dle itself when tested under these co"diliGns.
Mo41 72 Although the invention has been descril)ed in detail in the foregoing for the purpose of illusl~dtiGn, it is to be understood that such detail is solely for that purpose and that varidlions can be made therein by those skilled in the art without depa, li"g from the spirit and 5 scope of the invention except as it may be limited by the claims.
Mo41 72
BACKGROUNC~ OF THE INVENTION
Field of the Invention:
The present invention relates to polyurea cor"positiGns derived from polyphenyl polymethylene polyisocyanate and a select group of ar":. ,es.
5 Brief Desc,~iol1 of the Prior Art:
Non-sagyins~ (or thixotropic) cGmpositions are widely known and used col"n~ercially. Such ",ater;als are important bec~use they are very convenient to use in many applications. An example would be adhesives and sealanl~ used in autom~ti~/e manufacturing where 10 such formuhliol,s can be supplied and conveniel,lly manipulated in a low-viscosity liquid form but then applied to even vertical surfaces as a thick non-running ",aterial.
Polyureas are also generally known in the art. CG"")ar~d to polyu,~tl,al-e analogs polyureas can have superior physical 15 prope,lies such as high te",per~lure pe,rul",al,ce~ adl,esion oil and solvent ,t:sista"ce and tear sllellylll. Due to the very high reactivity of most amine cGr"pounds toward isocyandles polyurea formulaliol)s often have short gel-times resulting in short "pot-life" (or working time). Therefore polyurea co",posilions have been limited to 20 applications where very short gel-times are desi,able such as in reaction injection molding. In additiol~ be~llse of the linli~lion to a fewfast-r~acti"ghigh-mo'ecul~rweightpolyar":.,es thereactivityand viscosity profiles of polyurea formulations could not be manipulated surr,cie.,lly to provide non-sagging systems.
ksl/11 2994 U.S. 5,128,433 ~JisclQses thixutlupic polymer compositiGn - comprising the reaction product of aromdtic polyisocyandles such a low rnclecu'A~ weight polyisocyanales based on 4,4'-diisocyanato-di~he"yl~"eti,al,e, toluene diisocyanate or the like or their prepolymers, and one or more ar~l"dtic diar"i.,es. The con,positio"s are said to be useful in ",al~i"g cGdlings, sealanls, adhesive bonds and molds.
U.S. Patent 4,954,199 disclQses a structural n,el"ber comprising a laminate and an adhesive where said adhesive is the reaction product of a speciried proportion of polyur~ll,alle-urea forming components: (a) 100 parts by weight of at least one hydroxyl functional ",alerial having a molecular weight of at least 300 and a hydroxyl f~n~;tio"ality of at least 2 and which ",al~rial is pre~r~bly selected from the group consisli"g of polyether polyols, polyester polyols, polyester amide polyols, and polycalLGI,ate polyols; (b) 0.2 to 20 parts by weight of an aliphatic, ar~mdlic, and/or a cycloaliphatic diamine or triamine; and (c) an organic isocyanate in an amount sufficient to render the isocyanate index between about 70 and about 150, wherein said cGmponent (c) is not pr~r~a-,ted with any of the components (a) and (b).
U.S. ratent~ 5,164,473 and 5,204,439 disclQse low viscosily two-cGIllpGllellt filled poly~ ll,ane adl,esives which are useful as structural adhesives cGnl~ lg a low viscosity isocyanate con"~onenl in a quantity sufficient to provide an isocyanate index of about 100 to 150 comprising an organic polyisocyanate wherein up to 10 equivalent percent of the isocyanate groups of said polyisocyanate have been ",odified by r~actiGn with one or more isocyanate-reactive compounds; a low viscosity curative component cGmprisi"g 5 to 50 equivalent per~enl of a polyether polyol and/or a polyether terminated Mo4172 by aro",dlic amino groups having an equivalent weight gr~aler than 500 based on the total equivalents of amino and hydroxyl groups of the curative co",po,)ent; 50 to 95 equivalent perce,lt of one or more chain e,~lel)del~ col"~.risi"g from 50 to 100 per~;enl of the isocyanate-reactive equivalents based on the total equivalents of amino and hydroxyl groups of the equivalent component; and one or more isocyanate-reactive diamines or triamines in a quantity surricie. ,t to produce adequate r~sistance to flow when the isocyanate and curative components are mixed and wherein at least one of these components contains at least one filler in a total quantity of from about 10 to about 40 percent by weight of the filled polyurethane adhesive.
During automobile manufacturing structural adhesives that are used to bond polymeric autol"ob.'e panels such as fascia can be subjected to te",per~ res of about 200 deylees Cenligrade or higher.
At these high ter"perdtures many of the art-related adhesives such as polyur~ll,ane adhesives loose their i"ley,ity by foaming cracl~i"y and/or softening with a conse4uential loss in physical and other adl ,esive prupel lies.
As would be realized there is a need for structural adhesives that can w;tl,stand high temper~lures.
SUMMARY OF THF INVFI~TION
Su,~l.risingly it was found that by using amir,ocr~tonated polyethers it is now possiLI~ to prepare blends containing only polyamine chain extenders and amine-terminated soft-sey",enl compounds with a balanced reactivity of the amines toward isocyalldles. It is ll,erefore possible in ,urd~;tice to prepare non-sagging all-urea cor"positions. Thus the desirable physical properties of polyureas can now be combined with non-sagg;"g chara~terislics.
Mo41 72 As would be re~ ed pr~pa(atiG,) of such cG"")ositi~ns demand highly controllable reactivity in order to opli",i,e viscosity profile hGI~ogeneily gel-time working life and green sl,e"~tl,. An u,lbalanced reactivity of the amines can also result in agglo~erdliGn 5 of urea upon mixing with the isocyanate. This leads to inhomogeneous n,dler;als and unacceplable physical properties. By the presenl invention one avoids the above problems bec~llse it is now possi~lc to prepare all-amine blends of chain extenders and soft seg",enls which provide improved reactivities and physical properties.
In accorlJance with the forego:.,g the present invention encompasses a polyurea composition comprising the reaction product of: (a) a polyphenyl polymethylene polyisocyanate or a urea-",GJiried prepolymer ll,ert:of and (b) an isocyanate reactive component comprising amines consislil,g essentially of (i) ar"inocr~tondte 15 polyether and(ii)alow",ole~ weightarol"~licoraliphatic diamine. The polyurea cGmpositiol, of the invention exhibits improved sag resislance at room ten,per~t.lre. This is manifested as a small bead of the rea.;ti"g ",aterial placed on a vertical surface not flowing sagging or dri~ping to make the ",dterial convenient to use in the 20 field. The polyurea composition are char~cteri,ed by markedly improved ll,e""al pelr~""ance properties.
DETAII Fn DFSCRIPTION OF THE INVFI~ITION
The polyurea cGI"positi~n of the invention can be pr~par~d by ,eacti"g the polyphenyl polymethylene polyi-~Gcyanate or a modified-25 urea prepolymer thereof with the mixture of amines of the invention inan equivalent ratio of the isocyanate to the amine in the range of about 0.9 to 1.4:1 and pr~:fer~bly 1.1:1 to 1.3:1.
The polyphenyl polymethylene polyisocyanate or the urea ",od~ried prepolymer thereof usually has an isocyanate contenl of Mo-41 72 about 20 to 40 pr~ferably 28 to 33. It can be obtained by pl,osgenating aniline/formaldehyde condensaliGn products. Examples Ll~er~or and their Illelhod of plt:pardliGn can be found in literature references such as Polyu,etl,ane I landbool; 2nd Edition G. Oertel 5 Hanser Publishers Munich Vienna NewYork pp: 73-83 and U.S.
Patents 3 471 543 which are i"co,~or~ted herein by ,~f~r~nce.
The urea-",o-l riecl prepolymer can be prtpar~d by r~a~ ti"g the polymeric polyphenyl polymethylene polyisocyanate with an amine.
Examples thereof and their ",ell,od of preparation are disclosed in 10 U.S. Patent 5 164 473 which is incorporated herein by ,ererence. The isocyanate reactive co"~pG"enl is a mixture of amines useful herein collsislil,g essentially of an aminocrutonate polyether and a low molecular weight arc""atic or aliphatic diamine. The aminocr~lonale polyether has a molecular weight of 500 to 5000 and pr~fer~bly 1000 15 to 3000 and a functionality of 2 to 6 and pr~ferably 2 to 3. The aminocr~tolldle polyether can be pr~par~d by aminolysis of ~cetoacelylated polyols. Ekdlllples thereof and their method of pr~:par~lion can be found in literature le~r~"ces such as U.S. Patents 3 691 112 3 666 726 5 066 824 and 5 151 470 which are 20 incorporated herein by refel~l)ce.
The low mc'ecul-~ weight dian,i"e has a ",olec~'-r weight of about 60 to 400 and pr~rably 60 to 300. Exar"ple. of the low Illo'e~ r weight ar~n,dlic diamine is s~lected from the group c~nsisli"g of toluene diamine diethyltoluene diamine 4 4'-diphenyl-25 methane diamine l,i",ell,ylene glycol di-p-ar":.,ol,el,~oale and bis(4-n-butylaminophenyl) ",ell,ane. Examples of the low r",olec~ weight aliphatic diamine is selectecl from the group cGnsi ti"g of isophorone diamine 4 4'-diamino-3 3'-dimethyldicyclohexyl~"ethane piperd~i"e bis-(4-aminocyclohexyl) ",~tl,ane and ethylenediamine.
Mo4172 In the pr)cess for pr~pa,i"g the polyurea composiliGn, the polyphenyl polymethylene polyisocyanate or the urea "odiried prepolymer lher~of and the mixture of amine can be combined in any order. Typically, the resulting combination (blend) is subjected to 5 isocyanate ~ddition r~actiG" at a"lbi~nl or elevated temperatures of up to 150C and p,efe,~bly 110 to 135C. Solvents which are typically inert solvents can be used for ease of rea~;tiGn. Although catalysts are not ordinarily required, they can be used, if desired. The ~aotio" product comprises the polyurea colllposiliGn of the invention.
In the practice of the invention, the polyurea col"position can be fommulated with additives such as fillers, Pis ",euts, molecular sieves, catalysts, and auxilialies such as flow agents, surface-active additives, anti-foaming agents, dyes, UV-stabilizers, fungi~l~lic and ba.,~rio~l~lic s~ sl~nces, such as those described in European 15 Patent Application 81,701 at column 6, line 40 to column 9, line 31.
Suitable fillers, particularly for the high temperature application (ll,e""al properties), include minerals, e.g. silicate-containing minerals, such as alltiy~lite~ sel~el,ti"e, homblends, amphiboles, chrysotile, talc, mica and kieselguhr; metal oxides such as kaolin, aluminum 20 oxides, titanium oxides, and iron oxides; metal salts such as chalk and heavy spar (barium sulfate); inGlyan.c ~iy"~ents such as cadmium sulfide and zinc sulfide; and glass, asbeslos powder, carbon fibers, and the like. Pl~rer,~d fillers are s~ sl~nlially inert under the col,ditions encountered when the components of the invention are 25 mixed. The pr~fel,ed fillers are talc, wollastonite or clay. A
particularly pr~rer,ed filler is talc. Fillers may be used either individual or in ad",i~ re. The fillers are added to either or both of compGnent~
(a) and (b) in quantities totaling about 10 to about 40% by weight based on the total quantity of the filled adhesive.
Mo-41 72 _ S~ le auxiliary agents and additives may include, for example, catalysts for the polyisocyanate-polyaddilio" ,~a~;tiG", drying agents, surface-active additives, anti-foaming agents, pigments, dyes, UV stabilizers, and pl~-~lic;~er~i. Typically, drying agents that avoid 5 rollndliol1 of bubbles that adversely affect high ter"perdl-lre pelroll''ance. Plefer~bly the drying agents are molecular sieve zeolites that can be employed in an amount of 1 to 15 parts by weight per 100 parts of the polyether polyol. Specific but nonlimiting examples of the m~'ecll~^r sieves can be sodium aluminosilicate in 10 amir,ocr~tondled polyether or polyether polyol (1:1) or sodium aluminosilicate powder.
In the practice of the invention, the isocyanate component is mixed with the isocyanate-reactive cGr"pol)enl in a predetermined ratio designed to provide an isocyanate index of from 100 to 150.
15 The term "isocyanate index" is defi"ed as the quotient, multipliei by 100, of the number of isocyanate groups divided by the number of isocyanate-reactive groups.
The polyisocyanate and the mixture of ar"i"es of the present invention are char~ctt:ri~ed by low viscosities As used herein, the 20 term "low viscosity" refers to a BroekfiEld viscosity at 25C of less than about 20,000 mPa-s. Despite the low vi3cosity, the reactive components exhibit excell~"l sag rt:sislance when the isocyanate and polyol blend are mixed.
The filler, as well as the G~ nal additives and auxiliaries, can 25 be mixed with either or both of the isocyanate component and the isocyanate-reactive component but is pre~er~bly mixed with the isocyanate-reactive component. The compol)ents may be mixed by any of various known ~ lhods, including impi"gel"enl mixing and Mo41 72 -static mixing and they may be arp'.ei to the sub~l,dle to be bonded as thin films or in the form of beads.
The polyurea compositiGns can be used in adhesive caulking and sealanl apr'.c^tions. It is pr~selltly preferred to employ the 5 polyurea ColllpoSitiGn in adhesive applic~lions for bonding .lirrarel)l or similar sul,sl,alas. The adhesivc can be used to bond sub~l,dles suchassteel aluminum polyl"~ll,ane epoxyorfiber-r~ rorl;ed polyester. The process for bonding the sulJ~lldtas cor"prises applying the adhesive to a subject sul)~tldla and conlacti"~ the surface with a 10 surface of another substrate to which is optionally applied the adhesive. The adl,esive can be ar plied by any convenient means such as in,pi.,gel"ent mixing or static mixing.
This and other ~-speGts of the invention are further illuslldted but are not i"tended to be limited by the following examples in which 15 all parts and per~nlages are by weight unless ull,elwi3e specifiad.
FxAMpl FS
AMINOCROTONATF POI YFTHFR SYNTHFSIS:
An amir,ocr~tondla polyether was p,t:pared using the following pr~ced.lre. Poly(l~l,ametl,yl~neoxide) diol (75.96 parts equivalent 20 weight 500) was r~actad with tert-butyl~ceto~cet~le (24.04 parts) at 175C under vacuum. After four hours FTIR analysis illdi~ted conlplete loss of the OH absGr~lion at 3300 cm~~. The room te,nper~ture viscosity was 520 mPa-s. This ~ceto~cetylated product (85.5 parts) was r~actad with cyclohexylamine (14.5 parts) at 110C
25 under vacuum. After several hours the product was cooled to room te",p~rdture (1790 mPa-s at 25C).
Exar,l~ le 1:
An amine blend according to the invention was prapal-ad using 63.5 parts cyclohexylamir,ocrotol,dle polyether (described above); 4.6 Mo~172 -g parts Ethacure 300 (Ethyl Corp.); 1.5 parts bis-(4-aminocyclohexyl)-",~tl,ane; 7.0 parts sodium aluminosilicate powder; 23.4 parts talc powder. This blend was ble.,Jed de~ssed and ,~acted at a 128 index with a polymeric di~Jl,enylm~ll,d"e diisocyanate (2 4'-isomer 5 conlenl about 1.6% and NCO functionality about 2.8). The ,t:actio"
mixture was bag mixed to avoid incorpordtion of air bubbles and a 6 x 6" x 1/8" plaque was cast. After curing the ",atelial at 100C for one day the Shore D I lar~ll,ess was 55. The sofleni"g point as determined using ll,el"~G",echanical analysis (TMA) was 168C.
10 Example ~:
An amine blend according to the invention was p,t:pared using 85.9 parts cyclohexylamir,ocrutonale polyether (desc,iued above); 2.2 parts piper~i"e; 1.7 parts diethyltoluene diamine; 10.0 parts sodium aluminosilicate powder. This mixture was blended degAssed and 15 reacted with the polyphenyl polymethylene polyisocyanate descl iL,ed in Ex~l~lplo 1. The rea~;tiol) was carried out at an NCO/OH ratio of 130. The rea~liol) blend was mixed cast and cured as described above for Exar"pl~ 1. The Shore A l lardl,ess of the resultant plaque was 35.
20 Example 3:
An amine blend accor~ling to the invention was prepaled using 63.3 parts cyclohexylamir,oc,ùtonale polyether (descliL,ed above); 7.5 parts llilll~:lhyle.,eylycol di-p-aminobel,~oate (Polacure 740M Air Products); 1.5 parts bis-(4-aminocyclol,exyl) metl,ane; 4.0 parts 25 sodium aluminosilicate powder; 23.7 parts talc. The mixture was ble.l-Jed de~ssed and reacted at an index of 130 with the polymeric polyisocyanate descriued in Example 1. After blendi"~ ca:,ling and curing as descriL,ed above the ",alerial hardness was 56 Shore D.
Mo-4172 -l ~ Shear Testing:
Adhesion pe,rullllance of Examples 1 2 and 3 was screened by using the lap shear test metl,ûd (SAE J1525). Saln~ les were prepared using sheet molding compound plaques (4" x 6" x 0.125") 5 and were bol)ded togetl,er using metal spacer:~ to insure a bond thickness of 0.030 inches. The bond overlap was 1 inch. The bond surface of the sheet molding compound was buffed with a clean d~
cloth prior to bonding to remove suRace conta,ninants. The sar"pl-s were cured in an oven at 135C for one hour and then conditioned at 10 room temperature for one day. Test coupons (4 x 1 in.) were cut from the cured plaques using a diamond-tipped saw. Samples were tested at room l~n,peldlure (ca. 23C). The maxi",um load values and %
sub~tldte failure meas~"e",enl:j are all averaS~es of five samples.
Test results are shown in the table below.
ADHESION TESTING RESULTS
ROOM TEMPERATURE LAP SHEAR TESTS
AdhesiveMaxi",um Load (PSI) % Subslr~ate Failure Example 1 686 100 Exall,pl~ 2622 100 Example 3 606 100 The results above clearly i".Jicale that these all-urea adhesive of this invention provide ex~e"ont bond strength to sheet molding cGl"pound. The maximum load values of 606 to 686 PSI show that these materials give sufficient adhesion to be classi~ied as high-25 peRormance (or"structural") adhesives. In addition the percentsuLst,ale failure measu,~l"ent~ prove that the adhesive and adhesive bond are stronger than the sul,:,l,dle itself when tested under these co"diliGns.
Mo41 72 Although the invention has been descril)ed in detail in the foregoing for the purpose of illusl~dtiGn, it is to be understood that such detail is solely for that purpose and that varidlions can be made therein by those skilled in the art without depa, li"g from the spirit and 5 scope of the invention except as it may be limited by the claims.
Mo41 72
Claims (15)
1. A polyurea composition comprising:
(a) polyphenyl polymethylene polyisocyanate or a urea-modified prepolymer thereof and (b) an isocyanate reactive component comprising amines consisting essentially of:
(i) aminocrotonate polyether, and (ii) a low molecular weight aromatic or aliphatic diamine or a mixture thereof.
(a) polyphenyl polymethylene polyisocyanate or a urea-modified prepolymer thereof and (b) an isocyanate reactive component comprising amines consisting essentially of:
(i) aminocrotonate polyether, and (ii) a low molecular weight aromatic or aliphatic diamine or a mixture thereof.
2. The polyurea composition of Claim 1 wherein the equivalent ratio of the isocyanate to the amine is 0.9 to 1.4.
3. The polyurea composition of Claim 2 wherein amino-crotonate polyether has a molecular weight of 500 to 5000 and a functionality of 2 to 6.
4. The polyurea composition of Claim 3 wherein the aminocrotonate polyether is prepared by reacting a polyfunctional acetoacetic acid ester with an amine.
5. The polyurea composition of Claim 1 wherein the low molecular weight amine has a weight average molecular weight of about 60 to 400.
6. The polyurea composition of Claim 1 wherein the low molecular weight aliphatic diamine is selected from the group consisting of bis(4-aminocyclohexyl)methane, isophorone diamine, ethylene diamine, and 4,4'-diamino-3,3'-dimethyl(dicyclohexyl)-methane.
7. The polyurea composition of Claim 1 wherein the low molecular weight aromatic diamine is selected from the group consisting of diethyltoluenediamine 4,4'-diphenylmethane diamine, 1,3,5-triethyl-2,4-diaminobenzene trimethylene glycol di-p-amino-benzoate, bis(4-n-butylaminophenyl)methane, and di-(methylthio)-toluenediamine.
8. An adhesive containing the polyurea composition of Claim 1 and filler comprising a mineral present in an amount from about 10 to 40 parts per 100 parts of the weight of urea composition and the filler.
9. The adhesive of Claim 8 wherein the filler is selected from the group consisting of talc, wollastonite and clay.
10. The adhesive of Claim 8 further comprising drying agent which is a molecular sieve zeolite that is present in an amount from 1 to 15 parts per 100 parts polyether polyol.
11. The adhesive of Claim 10 wherein the molecular sieve is selected from the group consisting of sodium aluminosilicate in aminocrotonated polyether (1:1), and sodium aluminosilicate powder.
12. A process for bonding structural members comprising applying to a surface of a structural member the polyurea composition as recited in Claim 1, contacting said surface with a surface of another structural member which optionally has applied thereto the polyurea composition, followed by curing the polyurea composition.
13. The process of Claim 12 wherein the polyurea composition is cured at ambient or elevated temperatures.
14. The process of Claim 13 wherein the polyurea composition is cured at elevated temperatures of 90 to 150°C.
15. A structural member which is prepared by the process of Claim 12.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US35440194A | 1994-12-12 | 1994-12-12 | |
| US08/354,401 | 1994-12-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2163402A1 true CA2163402A1 (en) | 1996-06-13 |
Family
ID=23393180
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002163402A Abandoned CA2163402A1 (en) | 1994-12-12 | 1995-11-21 | Thixotropic polyurea compositions |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US5654085A (en) |
| CA (1) | CA2163402A1 (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19711528A1 (en) * | 1996-03-26 | 1997-11-06 | Relius Coatings Gmbh & Co | Strippable masking lacquer for etching metal surfaces |
| US6793864B1 (en) | 1997-02-26 | 2004-09-21 | Dunlop Sports | Polyurethane material for two and three piece golf balls |
| NZ505396A (en) * | 1997-12-03 | 2002-10-25 | Innovative Coatings Corp | Synthetic stucco system for a building |
| US7223181B2 (en) * | 1998-02-04 | 2007-05-29 | Taylormade-Adidas Golf Company | Polyurethane material for two and three piece golf balls and method |
| US7244384B1 (en) | 1998-02-04 | 2007-07-17 | Taylormade-Adidas Golf Company | Method for manufacturing two and three piece golf balls constructed from polyurethane material |
| US6539630B1 (en) | 1999-12-02 | 2003-04-01 | Fabick, Inc. | Method of adhesion of in situ vehicle bed liner |
| US6719646B2 (en) | 2000-01-25 | 2004-04-13 | Dunlop Slazenger Sports | Polyurethane covered three-piece golf ball |
| US6846532B1 (en) | 2001-02-15 | 2005-01-25 | Sonoco Development, Inc. | Laminate packaging material |
| US20040115414A1 (en) * | 2002-03-15 | 2004-06-17 | Joseph Wycech | Method for stiffening or reinforcing a member in a cost effective manner and a member which is made in accordance with the method |
| US8168281B2 (en) | 2006-10-27 | 2012-05-01 | Michelin Rechenche er Technique, S.A. | Polyurea adhesive |
| EP2614103B1 (en) | 2010-09-10 | 2015-04-15 | Invista Technologies S.a r.l. | Polyetheramines, compositions including polyetheramines, and methods of making |
| US8697188B2 (en) | 2011-09-02 | 2014-04-15 | Construction Research & Technology Gmbh | Polyurethane systems having non-sag and paintability |
| WO2013029889A1 (en) | 2011-09-02 | 2013-03-07 | Construction Research & Technology Gmbh | Polyurethane systems having non-sag paintability and primerless adhesion on concrete |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4444976A (en) * | 1982-12-20 | 1984-04-24 | The Goodyear Tire & Rubber Company | Sag resistant two component adhesive and sealant |
| US4954199A (en) * | 1986-05-30 | 1990-09-04 | Mobay Corporation | Two component polyurethane adhesive |
| US5143996A (en) * | 1987-08-20 | 1992-09-01 | Ashland Oil, Inc. | Primerless adhesive for fiberglass reinforced polyester substrates |
| US4994540A (en) * | 1990-01-16 | 1991-02-19 | Mobay Corporation | Sag resistant, unfilled, low viscosity urethane structural adhesive |
| US5164473A (en) * | 1990-01-16 | 1992-11-17 | Miles Inc. | Two-component polyurethane adhesive |
| US5204439A (en) * | 1990-01-16 | 1993-04-20 | Miles Inc. | Two-component polyurethane adhesive |
| US5128433A (en) * | 1991-06-04 | 1992-07-07 | Polytek Development Corp. | Thixotropic polymer compositions and process for use thereof |
| US5175228A (en) * | 1991-12-09 | 1992-12-29 | Gencorp Inc. | Two-component primerless urethane-isocyanurate adhesive compositions having high temperature resistance |
-
1995
- 1995-11-21 CA CA002163402A patent/CA2163402A1/en not_active Abandoned
-
1996
- 1996-02-20 US US08/604,118 patent/US5654085A/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| US5654085A (en) | 1997-08-05 |
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